催化剂控制的α-烷基烯基芳基芳烃的 1,2-和 1,1-芳基硼化反应。
Catalyst-Controlled 1,2- and 1,1-Arylboration of α-Alkyl Alkenyl Arenes.
机构信息
Department of Chemistry, Indiana University, 800 E. Kirkwood Avenue, Bloomington, IN, 47405, USA.
出版信息
Angew Chem Int Ed Engl. 2019 Feb 4;58(6):1719-1723. doi: 10.1002/anie.201812533. Epub 2019 Jan 9.
Abstract
Two methods are reported for the 1,2- and 1,1-arylboration of α-methyl vinyl arenes. In the case of 1,2-arylboration, the formation of a quaternary center occurred through a rare cross-coupling reaction of a tertiary organometallic complex. 1,1-Arylboration was enabled by catalyst optimization and occurred through a β-hydride elimination/reinsertion cascade. Enantioselective variants of both processes are presented as well as mechanistic investigations.
摘要
本文报道了两种方法用于α-甲基乙烯基芳烃的 1,2-和 1,1-芳基硼化。在 1,2-芳基硼化的情况下，通过罕见的三级有机金属配合物交叉偶联反应形成了一个季碳原子中心。通过催化剂优化实现了 1,1-芳基硼化，并通过β-氢化物消除/插入级联反应进行。本文还介绍了这两种方法的对映选择性变体以及机理研究。
相似文献
1
Catalyst-Controlled 1,2- and 1,1-Arylboration of α-Alkyl Alkenyl Arenes.催化剂控制的α-烷基烯基芳基芳烃的 1,2-和 1,1-芳基硼化反应。
Angew Chem Int Ed Engl. 2019 Feb 4;58(6):1719-1723. doi: 10.1002/anie.201812533. Epub 2019 Jan 9.
2
Catalytic Enantioselective Arylboration of Alkenylarenes.催化对映选择性烯基芳基硼化反应。
Angew Chem Int Ed Engl. 2017 Jan 16;56(3):851-855. doi: 10.1002/anie.201609844. Epub 2016 Dec 21.
3
Arylboration of alkenes by cooperative palladium/copper catalysis.钯/铜协同催化烯烃芳基化反应。
J Am Chem Soc. 2014 May 28;136(21):7567-70. doi: 10.1021/ja5029556. Epub 2014 May 14.
4
Ligand-Controlled Regiodivergent Copper-Catalyzed Alkylboration of Alkenes.配体控制的铜催化烯烃区域选择性烷基硼化反应。
Angew Chem Int Ed Engl. 2015 Oct 26;54(44):12957-61. doi: 10.1002/anie.201506713. Epub 2015 Sep 4.
5
Nickel-Catalyzed Stereoselective Arylboration of Unactivated Alkenes.镍催化的非活化烯烃的立体选择性芳基化反应。
J Am Chem Soc. 2018 Jan 10;140(1):159-162. doi: 10.1021/jacs.7b12160. Epub 2017 Dec 22.
6
Copper-Catalyzed Borylacylation of Activated Alkenes with Acid Chlorides.铜催化的酰氯与活化烯烃的硼酰化反应。
Angew Chem Int Ed Engl. 2017 Oct 16;56(43):13314-13318. doi: 10.1002/anie.201707323. Epub 2017 Sep 18.
7
Enantioselective Hydroalkenylation of Olefins with Enol Sulfonates Enabled by Dual Copper Hydride and Palladium Catalysis.双铜氢化物和钯催化促进的烯醇砜对烯烃的对映选择性氢烯丙基化反应。
J Am Chem Soc. 2021 Apr 14;143(14):5330-5335. doi: 10.1021/jacs.1c02117. Epub 2021 Mar 30.
8
Enantioselective 1,1-arylborylation of alkenes: merging chiral anion phase transfer with Pd catalysis.烯烃的对映选择性1,1-芳基硼化反应：手性阴离子相转移与钯催化的结合
J Am Chem Soc. 2015 Mar 11;137(9):3213-3216. doi: 10.1021/jacs.5b00344. Epub 2015 Feb 27.
9
Enantioselective Preparation of Arenes with β-Stereogenic Centers: Confronting the 1,1-Disubstituted Olefin Problem Using CuH/Pd Cooperative Catalysis.对映选择性制备具有β-手性中心的芳烃：使用 CuH/Pd 协同催化解决 1,1-二取代烯烃问题。
Angew Chem Int Ed Engl. 2020 Sep 7;59(37):16128-16132. doi: 10.1002/anie.202004414. Epub 2020 Jun 30.
10
Copper-mediated, palladium-catalyzed coupling of thiol esters with aliphatic organoboron reagents.铜介导、钯催化硫醇酯与脂肪族有机硼试剂的偶联反应。
J Org Chem. 2004 May 14;69(10):3554-7. doi: 10.1021/jo049964p.
引用本文的文献
1
Palladium-Catalyzed Aerobic Alkene Arylboration: Coupling Aryl Boronic Acids, Alkenes, and Bis(pinacol)diboron.钯催化需氧烯烃芳基硼化反应：芳基硼酸、烯烃与双（频哪醇）二硼的偶联反应
ACS Catal. 2025 Aug 15;15(16):14564-14574. doi: 10.1021/acscatal.5c03926. Epub 2025 Aug 7.
2
Approach Toward Stereoselective α-Arylation by Pd/Cu-Catalyzed Arylboration of Electron Deficient Alkenes.通过钯/铜催化缺电子烯烃的芳基硼化实现立体选择性α-芳基化的方法
Angew Chem Int Ed Engl. 2025 May 26;64(22):e202424073. doi: 10.1002/anie.202424073. Epub 2025 Mar 27.
3
Synthesis of (±)-Phyltetralin by Cu/Pd-Catalyzed Arylboration.通过铜/钯催化芳基硼化反应合成（±）-叶状四氢萘
Synlett. 2023 Nov;34(18):2197-2199. doi: 10.1055/s-0041-1738434. Epub 2023 Apr 5.
4
A general approach to stereospecific Pd-catalyzed cross-coupling reactions of benzylic stereocenters.一种苄基立体中心的立体专一性钯催化交叉偶联反应的通用方法。
Chem Sci. 2023 Nov 24;14(48):14124-14130. doi: 10.1039/d3sc04519f. eCollection 2023 Dec 13.
5
Cu/Pd-catalyzed arylboration of a 1-silyl-1,3-cyclohexadiene for stereocontrolled and diverse cyclohexane/ene synthesis.铜/钯催化的1-硅基-1,3-环己二烯的芳基硼化反应用于立体控制的多样环己烷/烯的合成。
Chem Sci. 2023 Sep 13;14(38):10467-10470. doi: 10.1039/d3sc02536e. eCollection 2023 Oct 4.
6
Pd-Catalyzed 1,3-Alkenylarylation of Skipped Diene via Metal Migration.钯催化的通过金属迁移实现的跳跃二烯的1,3-烯基芳基化反应。
ACS Omega. 2023 May 25;8(22):19912-19916. doi: 10.1021/acsomega.3c01839. eCollection 2023 Jun 6.
7
Arylboration of Enecarbamates for the Synthesis of Borylated Saturated N-Heterocycles.烯基碳酰胺芳基化反应合成硼化饱和 N-杂环化合物。
Angew Chem Int Ed Engl. 2022 Nov 14;61(46):e202212117. doi: 10.1002/anie.202212117. Epub 2022 Oct 17.
8
Cooperative Pd/Cu Catalysis for Alkene Arylboration: Opportunities for Divergent Reactivity.用于烯烃芳基硼化的协同钯/铜催化：不同反应性的机遇
ACS Catal. 2022 Feb 4;12(3):2058-2063. doi: 10.1021/acscatal.1c05696. Epub 2022 Jan 24.
9
Catalytic Arylboration of Spirocyclic Cyclobutenes: Rapid Access to Highly Substituted Spiro[3.n]alkanes.螺环环丁烯的催化芳基硼化反应：快速合成高度取代的螺[3.n]烷烃
ACS Catal. 2021 Oct 15;11(20):12815-12820. doi: 10.1021/acscatal.1c03491. Epub 2021 Oct 6.
10
Controllable access to trifluoromethyl-containing indoles and indolines: palladium-catalyzed regioselective functionalization of unactivated alkenes with trifluoroacetimidoyl chlorides.含三氟甲基吲哚和二氢吲哚的可控合成：钯催化未活化烯烃与三氟乙酰亚胺酰氯的区域选择性官能化反应
Chem Sci. 2022 Mar 3;13(12):3526-3532. doi: 10.1039/d2sc00546h. eCollection 2022 Mar 24.
本文引用的文献
1
Copper-boryl mediated organic synthesis.铜-硼试剂介导的有机合成。
Chem Soc Rev. 2018 Oct 1;47(19):7477-7494. doi: 10.1039/c7cs00816c.
2
Cu-catalyzed enantioselective synthesis of tertiary benzylic copper complexes and their addition to carbonyl compounds.铜催化的对映选择性合成叔苄基铜配合物及其对羰基化合物的加成反应。
Chem Sci. 2018 Apr 30;9(22):4992-4998. doi: 10.1039/c8sc00827b. eCollection 2018 Jun 14.
3
Nickel-Catalyzed Stereoselective Arylboration of Unactivated Alkenes.镍催化的非活化烯烃的立体选择性芳基化反应。
J Am Chem Soc. 2018 Jan 10;140(1):159-162. doi: 10.1021/jacs.7b12160. Epub 2017 Dec 22.
4
Mechanism-based enhancement of scope and enantioselectivity for reactions involving a copper-substituted stereogenic carbon centre.基于机制的增强，扩大了涉及铜取代手性碳中心的反应的范围和对映选择性。
Nat Chem. 2018 Jan;10(1):99-108. doi: 10.1038/nchem.2861. Epub 2017 Oct 2.
5
Copper-Catalyzed Alkynylboration of Alkenes with Diboron Reagents and Bromoalkynes.铜催化烯烃与二硼试剂及溴代炔烃的炔基硼化反应
Chem Asian J. 2017 Nov 16;12(22):2884-2888. doi: 10.1002/asia.201701176. Epub 2017 Oct 23.
6
Mechanistic Investigations of the Pd(0)-Catalyzed Enantioselective 1,1-Diarylation of Benzyl Acrylates.钯（0）催化的苯丙烯酸酯的对映选择性 1,1-二芳基化反应的机理研究。
J Am Chem Soc. 2017 Sep 13;139(36):12688-12695. doi: 10.1021/jacs.7b06917. Epub 2017 Aug 30.
7
Palladium-Catalyzed Negishi Coupling of α-CF Oxiranyl Zincate: Access to Chiral CF-Substituted Benzylic Tertiary Alcohols.钯催化的α-CF 氧化环锌试剂的 Negishi 偶联反应：手性 CF 取代苄基叔醇的合成。
J Am Chem Soc. 2017 Aug 23;139(33):11590-11594. doi: 10.1021/jacs.7b06630. Epub 2017 Aug 10.
8
Enabling the Cross-Coupling of Tertiary Organoboron Nucleophiles through Radical-Mediated Alkyl Transfer.通过自由基介导的烷基转移实现三级有机硼亲核试剂的交叉偶联。
J Am Chem Soc. 2017 Jul 26;139(29):9847-9850. doi: 10.1021/jacs.7b06288. Epub 2017 Jul 18.
9
Catalyst Controlled Regiodivergent Arylboration of Dienes.催化剂控制的二烯芳烃区域选择性硼化反应。
J Am Chem Soc. 2017 Jul 26;139(29):9823-9826. doi: 10.1021/jacs.7b05477. Epub 2017 Jul 12.
10
Regioselective Arylboration of Isoprene and Its Derivatives by Pd/Cu Cooperative Catalysis.钯/铜协同催化对异戊二烯及其衍生物的区域选择性芳基化。
J Am Chem Soc. 2017 Jun 14;139(23):7721-7724. doi: 10.1021/jacs.7b04024. Epub 2017 Jun 5.
Zotero 插件